CN1935659A - Method for preparing lead zirconatetianate nano powder - Google Patents
Method for preparing lead zirconatetianate nano powder Download PDFInfo
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- CN1935659A CN1935659A CN 200610053900 CN200610053900A CN1935659A CN 1935659 A CN1935659 A CN 1935659A CN 200610053900 CN200610053900 CN 200610053900 CN 200610053900 A CN200610053900 A CN 200610053900A CN 1935659 A CN1935659 A CN 1935659A
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- zirconium
- zirconate titanate
- lead
- lead zirconate
- titanium
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- 238000000034 method Methods 0.000 title abstract description 6
- 239000011858 nanopowder Substances 0.000 title description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 57
- 239000010936 titanium Substances 0.000 claims abstract description 49
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 20
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 20
- 229910020684 PbZr Inorganic materials 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 17
- 229910052451 lead zirconate titanate Inorganic materials 0.000 claims description 17
- 229910021645 metal ion Inorganic materials 0.000 claims description 17
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000000975 co-precipitation Methods 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 230000001143 conditioned effect Effects 0.000 claims description 5
- 229960004756 ethanol Drugs 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000010335 hydrothermal treatment Methods 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 1
- 229920002451 polyvinyl alcohol Polymers 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 2
- 230000006911 nucleation Effects 0.000 abstract 2
- 238000010899 nucleation Methods 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 230000001089 mineralizing effect Effects 0.000 abstract 1
- 241000894007 species Species 0.000 description 8
- 239000002904 solvent Substances 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005094 computer simulation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a lead zirconate titanate nano powder preparing method, mainly characterized in introducing reacting materials in a codeposition form of zirconium, titanium and lead, using mineralizing agent concentration to control nucleation number, and implementing hydrothermal synthesis of lead zirconate titanate nano powder. Firstly it prepares hydroxide codeposition of zirconium, titanium and lead as hydrothermal reacting materials, then selects proper potassium hydroxide concentration to increase nucleation number, inhibits growth of grains, and produces lead zirconate titanate nano powder with grain size not greater than 10 nm by hydrothermal reaction at 160-240 deg.C high temperature and high pressure. And the product has stable quality, high purity, and good grain dispersivity. And the process is simple, easy to control, no-pollution, low-cost and easy for scale production.
Description
Technical field
The present invention relates to a kind of preparation method of lead zirconate titanate powder, belong to field of inorganic nonmetallic material.
Background technology
Pb-based lanthanumdoped zirconate titanates (PbZr
xTi
1-xO
30＜x＜1, PZT) be the 1950's Shirane and his co-worker at first invent, have higher Curie temperature (about 380 ℃) and piezo-electric modulus (about 600pm/V), thereby has very consequence in the electric mechanical production, be preparation non-volatility ferroelectric storer, and the base mateiral of most of electro-mechanical devices such as sonar, nautical receiving set, ultra-sonic generator, high volt generator and fine position device.PZT remains research and uses maximum ferroelectric, piezoelectric up to now.
Experiment and Computer simulation results show when the size of ferroelectric material reaches nanoscale, many special performances occur.People such as the Park of Harvard University synthesize the BaTiO of diameter in the 5-60 nanometer by the control to bimetal alkoxide liquid phase cracking process
3Nanometer rod, and under the two-beam scanning electronic microscope, pass through the electrostatic attraction extraction electrode, measure and studied BaTiO
3The ferroelectric properties of nanometer rod.Discover still have the good ferroelectric performance when diameter of barium titanate nano line is 10nm, can induce to form 100nm
2Non-volatile polarization electricdomain, the coercive electric field intensity of polarization reversal is about 7kV/cm, the hold-time of induced polarization was above 5 days.This just means that also can utilize ferroelectric nano-wire to prepare storage density reaches 1024G/cm
2Non-volatility memorizer, be 2 orders of magnitude of existing memory density.People such as professor Fu of Univ. of Arkansas utilize first principle, The study of computer simulation the performance of Pb-based lanthanumdoped zirconate titanates nanostructure.Find when lead zirconate-titanate ferroelectric nano particle yardstick during the bistable state phase transformation that still shows low temperature structure near 3.2nm.Utilize this performance, can prepare the non-volatility ferroelectric storer that storage density reaches 60 * 1012bit/ inch, 5 that are existing memory density more than the order of magnitude.Therefore, synthetic particle scale is significant to the miniaturization and the exploitation of quickening large vol non-volatility memorizer that promote microelectronic device near the lead zirconate titanate powder of 3.2nm.But lead zirconate titanate powder synthetic minimum particle size is professor Zou of a georgia ,u.s.a engineering institute report at present, and they utilize sol-gel method synthetic PbZr
0.54Ti
0.46O
3The nano particle yardstick is about 17 ± 3nm, much larger than the PZT granularity that can be used to prepare the high-density ferroelectric memory of professor's Fu report.
Summary of the invention
The object of the present invention is to provide a kind of technology simple, the granularity that is easy to control is not more than the preparation method of Pb-based lanthanumdoped zirconate titanates (PZT) powder of 10 nanometers.
Pb-based lanthanumdoped zirconate titanates (PZT) nano-powder of the present invention's preparation, its chemical formula is: PbZr
xTi
1-xO
3, 0.4≤x≤0.6.
The preparation method may further comprise the steps:
1) by the chemical formula PbZr that desires the synthetic lead zirconate titanate powder
xTi
1-xO
3, 0.4≤x≤0.6, metering takes by weighing zirconium oxychloride and excessive 0～15% and takes by weighing lead nitrate, is dissolved in deionized water together, form the aqueous solution that contains zirconium oxychloride and lead nitrate, and the concentration of metal ion is 0.05～0.20M/L in the regulator solution;
2) take by weighing tetrabutyl titanate by the chemical formula metering of desiring the synthetic PZT powder and be dissolved in dehydrated alcohol, and the Ti in the regulator solution
4+Ionic concn is 0.05～0.2M/L;
3) the tetrabutyl titanate ethanol solution is added in the aqueous solution that contains zirconium oxychloride and lead nitrate under the state that stirs, formation contains the mixing solutions of zirconium, titanium and plumbous three metal ion species, and is 0.08～0.30M/L with the concentration of metal ions in the deionized water regulator solution;
4) with the mixing solutions of three prepared metal ion species under the state that stirs, be added drop-wise in the ammonia soln that concentration is 0.10～0.30M/L, precipitation is filtered, washed with de-ionized water is filtered the co-precipitation that obtains zirconium, titanium, plumbous oxyhydroxide;
5) with zirconium, titanium, plumbous oxyhydroxide co-precipitation, mineralizer potassium hydroxide joins in the inner bag of autoclave, reach reactor inner bag volumetrical 1/3～3/4 with the reaction mass in the deionized water conditioned reaction still inner bag, stirred at least 5 minutes, wherein to be scaled the molecular volume mark of desiring the synthetic Pb-based lanthanumdoped zirconate titanates be 0.05～2M/L for zirconium, titanium, plumbous oxyhydroxide co-precipitation, the molecular volume mark of potassium hydroxide is 2～6M/L, and molecular volume fractional volume radix is the volume of material in all introducing reactor inner bags;
6) the reactor inner bag that will dispose reaction mass places autoclave, sealing, be incubated 4～36 hours down at 160～240 ℃ and carry out hydrothermal treatment consists, reduce to room temperature then, take out reaction product, filter, use oxalic acid solution, the washed with de-ionized water of deionized water, 0.1～1.0M/L successively, with the dehydrated alcohol dehydration, dry under 60 ℃～100 ℃ temperature again, obtain lead zirconate titanate powder.
In the preparation process of the present invention, the said potassium hydroxide of step 5) joins in the reactor with Granular forms, perhaps potassium hydroxide is dissolved in the deionized water, joins in the reactor with the form of solution.
Among the present invention, the purity of said tetrabutyl titanate, zirconium oxychloride, lead nitrate, potassium hydroxide, ammoniacal liquor and dehydrated alcohol all is not less than chemical pure.
The present invention introduces reaction mass with the form of zirconium, titanium, plumbous co-precipitation, and utilizes the mineralizer (potassium hydroxide) of higher concentration to increase to nuclear volume, grows up thereby suppress particle, and the realization granularity is not more than the hydro-thermal of the lead zirconate titanate powder of 10nm and synthesizes.In the technological process of the present invention, be in order to remove chlorion and nitrate ion to the cleaning of coprecipitate, the number of times of cleaning is decided on cleaning performance.Cleaning to the hydro-thermal synthetic product is for mineralizer KOH fully being separated with synthetic PZT nano-powder, obtaining the PZT powder of pure phase at last.Adopting the dehydrated alcohol dehydration and be not higher than 100 ℃ oven dry, is in order to obtain the PZT nano-powder of favorable dispersity.
Beneficial effect of the present invention is: technological process is simple, is easy to control, non-environmental-pollution, and cost is low, is easy to large-scale production.The lead zirconate titanate powder granularity that makes is not more than 10nm, constant product quality, purity height, powder granule good dispersity.
Description of drawings
Fig. 1 is synthetic Pb-based lanthanumdoped zirconate titanates PbZr of the present invention
0.52Ti
0.48O
3The XRD figure of ground rice body spectrum in receiving;
Fig. 2 is synthetic Pb-based lanthanumdoped zirconate titanates PbZr of the present invention
0.52Ti
0.48O
3The transmission electron microscope of nano-powder (TEM) photo and choose diffraction (SEAD) style.
Embodiment
Further specify the present invention below in conjunction with embodiment.
Example 1
By the synthetic Pb-based lanthanumdoped zirconate titanates PbZr of following processing step
0.52Ti
0.48O
3Nano-powder.
1) by desiring synthetic PbZr
0.52Ti
0.48O
3The stoichiometry of nano-powder takes by weighing tetrabutyl titanate and is dissolved in the anhydrous ethanol solvent, and the Ti in the regulator solution
4+Ionic concn is 0.08M/L;
Take by weighing zirconium oxychloride and excessive 10% and take by weighing lead nitrate and be dissolved in together in the deionized water solvent, compound concentration is zirconium oxychloride, the lead nitrate mixed aqueous solution of 0.15M/L;
2) under the state that stirs, the tetrabutyl titanate ethanol solution is quickly poured in the aqueous solution that contains zirconium oxychloride and lead nitrate, and is 0.10M/L, obtain containing Zr with the concentration of metal ions in the deionized water regulator solution
4+, Ti
4+, Pb
2+The mixing solutions of three metal ion species;
3) will contain Zr
4+, Ti
4+, Pb
2+The mixing solutions of three metal ion species is added drop-wise in the ammonia soln that concentration is 0.15M/L under the state that stirs, and precipitation is filtered, and uses washed with de-ionized water 6 times, the zirconium of be removed chlorine and nitrate ion, titanium, plumbous oxyhydroxide co-precipitation;
4) plumbous oxyhydroxide co-precipitation of zirconium, titanium and the sheet mineralizer KOH with the step 3) preparation joins in the autoclave polytetrafluoroethylliner liner that the inner bag volume is 60mL, reach reactor inner bag volumetrical 2/3 with the reaction mass in the deionized water conditioned reaction still inner bag, in the material of introducing the reactor inner bag, zirconium, titanium, plumbous oxyhydroxide co-precipitation are scaled desires synthetic PbZr
0.52Ti
0.48O
3The molecular volume mark be 0.1M/L, the molecular volume mark of KOH is 4M/L, molecular volume fractional volume radix is that all introduce the volume of material in reactor inner bags; Magnetic agitation 30 minutes;
5) inner bag that reaction mass will be housed places the reactor of stainless steel casing, and sealing places electric furnace again, and 200 ℃ of constant temperature thermal treatments are after 12 hours, takes out to place air to lower the temperature naturally.After the temperature of question response still is reduced to room temperature, open reactor, reaction product is taken out, filter, with washed with de-ionized water 5 times, clean 3 times with the oxalic acid solution of 0.1M/L, use washed with de-ionized water again 6 times, dehydrated alcohol dehydration 2 times, 60 ℃ of oven dry, obtaining granularity is the Pb-based lanthanumdoped zirconate titanates PbZr of 3～6nm
0.52Ti
0.48O
3Nano-powder.Its XRD figure spectrum is seen Fig. 1, and its transmission electron microscope (TEM) photo is seen Fig. 2.
Example 2
By the synthetic Pb-based lanthanumdoped zirconate titanates PbZr of following processing step
0.40Ti
0.60O
3Nano-powder.
1) by desiring synthetic PbZr
0.4Ti
0.60O
3The stoichiometry of nano-powder takes by weighing tetrabutyl titanate and is dissolved in the anhydrous ethanol solvent, and the Ti in the regulator solution
4+Ionic concn is 0.1M/L;
Take by weighing zirconium oxychloride and excessive 10% and take by weighing lead nitrate and be dissolved in together in the deionized water solvent, compound concentration is zirconium oxychloride, the lead nitrate mixed aqueous solution of 0.2M/L;
2) under the state that stirs, the tetrabutyl titanate ethanol solution is quickly poured in the aqueous solution that contains zirconium oxychloride and lead nitrate, and is 0.15M/L, obtain containing Zr with the concentration of metal ions in the deionized water regulator solution
4+, Ti
4+, Pb
2+The mixing solutions of three metal ion species;
(1) will contain Zr
4+, Ti
4+, Pb
2+The mixing solutions of three metal ion species is added drop-wise in the ammonia soln that concentration is 0.15M/L under the state that stirs, and precipitation is filtered, and uses washed with de-ionized water 6 times, the zirconium of be removed chlorine and nitrate ion, titanium, plumbous oxyhydroxide co-precipitation;
(2) the plumbous oxyhydroxide co-precipitation of zirconium, titanium, the mineralizer KOH solution with the step 3) preparation joins in the autoclave polytetrafluoroethylliner liner that the inner bag volume is 60mL, reach reactor inner bag volumetrical 3/4 with the reaction mass in the deionized water conditioned reaction still inner bag, in the material of introducing the reactor inner bag, zirconium, titanium, plumbous oxyhydroxide co-precipitation are scaled desires synthetic PbZr
0.4Ti
0.60O
3The molecular volume mark be 0.15M/L, the molecular volume mark of KOH is 2M/L, molecular volume fractional volume radix is that all introduce the volume of material in reactor inner bags; Magnetic agitation 30 minutes;
(3) inner bag that reaction mass will be housed places the reactor of stainless steel casing, and sealing places electric furnace again, 200 ℃ of constant temperature thermal treatments are after 16 hours, and taking-up places air to lower the temperature naturally, after the temperature of question response still is reduced to room temperature, open reactor, reaction product is taken out, filter, with washed with de-ionized water 5 times, oxalic acid solution with 0.1M/L cleans 3 times, uses washed with de-ionized water again 6 times, dehydrated alcohol dehydration 2 times, 60 ℃ of oven dry, obtaining granularity is the Pb-based lanthanumdoped zirconate titanates PbZr of 5～10nm
0.4Ti
0.60O
3Nano-powder.
Example 3
By the synthetic Pb-based lanthanumdoped zirconate titanates PbZr of following processing step
0.60Ti
0.40O
3Nano-powder.
1) by desiring synthetic PbZr
0.60Ti
0.40O
3The stoichiometry of nano-powder takes by weighing tetrabutyl titanate and is dissolved in the anhydrous ethanol solvent, and the Ti4+ ionic concn in the regulator solution is 0.2M/L;
Take by weighing zirconium oxychloride and lead nitrate and be dissolved in together in the deionized water solvent, compound concentration is zirconium oxychloride, the lead nitrate mixed aqueous solution of 0.05M/L;
2) under the state that stirs, the tetrabutyl titanate ethanol solution is quickly poured in the aqueous solution that contains zirconium oxychloride and lead nitrate, and is 0.3M/L, obtain containing Zr with the concentration of metal ions in the deionized water regulator solution
4+, Ti
4+, Pb
2+The mixing solutions of three metal ion species;
(4) will contain Zr
4+, Ti
4+, Pb
2+The mixing solutions of three metal ion species is added drop-wise in the ammonia soln that concentration is 0.3M/L under the state that stirs, and precipitation is filtered, and uses washed with de-ionized water 6 times, the zirconium of be removed chlorine and nitrate ion, titanium, plumbous oxyhydroxide co-precipitation;
(5) the plumbous oxyhydroxide co-precipitation of zirconium, titanium, mineralizer KOH and the PVA solution with the step 3) preparation joins in the autoclave polytetrafluoroethylliner liner that the inner bag volume is 60mL, reach reactor inner bag volumetrical 3/4 with the reaction mass in the deionized water conditioned reaction still inner bag, in the material of introducing the reactor inner bag, zirconium, titanium, plumbous oxyhydroxide co-precipitation are scaled desires synthetic PbZr
0.60Ti
0.40O
3The molecular volume mark be 0.05M/L, the molecular volume mark of KOH is 6M/L, molecular volume fractional volume radix is that all introduce the volume of material in reactor inner bags; Magnetic agitation 30 minutes;
(6) inner bag that reaction mass will be housed places the reactor of stainless steel casing, and sealing places electric furnace again, 200 ℃ of constant temperature thermal treatments are after 36 hours, and taking-up places air to lower the temperature naturally, after the temperature of question response still is reduced to room temperature, open reactor, reaction product is taken out, filter, with washed with de-ionized water 5 times, oxalic acid solution with 0.1M/L cleans 3 times, uses washed with de-ionized water again 6 times, dehydrated alcohol dehydration 2 times, 100 ℃ of oven dry, obtaining granularity is the Pb-based lanthanumdoped zirconate titanates PbZr of 2～6nm
0.60Ti
0.40O
3Nano-powder.
Claims (4)
1. the preparation method of a lead zirconate titanate powder is characterized in that may further comprise the steps:
1) by the chemical formula PbZr that desires the synthetic lead zirconate titanate powder
xTi
1-xO
3, 0.4≤x≤0.6, metering takes by weighing zirconium oxychloride and excessive 0～15% and takes by weighing lead nitrate, is dissolved in deionized water together, form the aqueous solution that contains zirconium oxychloride and lead nitrate, and the concentration of metal ion is 0.05～0.20M/L in the regulator solution;
2) take by weighing tetrabutyl titanate by the chemical formula metering of desiring the synthetic PZT powder and be dissolved in dehydrated alcohol, and the Ti in the regulator solution
4+Ionic concn is 0.05～0.2M/L;
3) the tetrabutyl titanate ethanol solution is added in the aqueous solution that contains zirconium oxychloride and lead nitrate under the state that stirs, formation contains the mixing solutions of zirconium, titanium and plumbous three metal ion species, and is 0.08～0.30M/L with the concentration of metal ions in the deionized water regulator solution;
4) with the mixing solutions of three prepared metal ion species under the state that stirs, be added drop-wise in the ammonia soln that concentration is 0.10～0.30M/L, precipitation is filtered, washed with de-ionized water is filtered the co-precipitation that obtains zirconium, titanium, plumbous oxyhydroxide;
5) with zirconium, titanium, plumbous oxyhydroxide co-precipitation, mineralizer potassium hydroxide joins in the inner bag of autoclave, reach reactor inner bag volumetrical 1/3～3/4 with the reaction mass in the deionized water conditioned reaction still inner bag, stirred at least 5 minutes, wherein to be scaled the molecular volume mark of desiring the synthetic Pb-based lanthanumdoped zirconate titanates be 0.05～2M/L for zirconium, titanium, plumbous oxyhydroxide co-precipitation, the molecular volume mark of potassium hydroxide is 2～6M/L, and molecular volume fractional volume radix is the volume of material in all introducing reactor inner bags;
6) the reactor inner bag that will dispose reaction mass places autoclave, sealing, be incubated 4～36 hours down at 160～240 ℃ and carry out hydrothermal treatment consists, reduce to room temperature then, take out reaction product, filter, use oxalic acid solution, the washed with de-ionized water of deionized water, 0.1～1.0M/L successively, with the dehydrated alcohol dehydration, dry under 60 ℃～100 ℃ temperature again, obtain lead zirconate titanate powder.
2. the preparation method of lead zirconate titanate powder according to claim 1 is characterized in that potassium hydroxide joins in the reactor with Granular forms in the step 5), perhaps potassium hydroxide is dissolved in the deionized water, joins in the reactor with the form of solution.
3. the preparation method of lead zirconate titanate powder according to claim 1 is characterized in that the purity of said tetrabutyl titanate, zirconium oxychloride, lead nitrate, potassium hydroxide, polyvinyl alcohol and ammoniacal liquor and dehydrated alcohol all is not less than chemical pure.
4. the preparation method of lead zirconate titanate powder according to claim 1, prepared lead zirconate titanate powder granularity is not more than 10nm.
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|---|---|---|---|
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|---|---|---|---|
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| CN100534905C CN100534905C (en) | 2009-09-02 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101319383B (en) * | 2008-04-25 | 2010-11-17 | 浙江大学 | Preparation method of nanometer barium zirconate |
| CN101935216A (en) * | 2010-08-29 | 2011-01-05 | 青岛理工大学 | Method for preparing lithium niobium titanium microwave dielectric ceramic powder by hydrothermal method |
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| US8853116B2 (en) | 2006-08-02 | 2014-10-07 | Eestor, Inc. | Method of preparing ceramic powders |
| CN105424672A (en) * | 2014-09-04 | 2016-03-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Non-stoichiometric oxide SERS substrate and preparation method thereof |
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2006
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| US8853116B2 (en) | 2006-08-02 | 2014-10-07 | Eestor, Inc. | Method of preparing ceramic powders |
| US10239792B2 (en) | 2006-08-02 | 2019-03-26 | Eestor, Inc. | Method of preparing ceramic powders |
| CN101319383B (en) * | 2008-04-25 | 2010-11-17 | 浙江大学 | Preparation method of nanometer barium zirconate |
| CN102333724A (en) * | 2009-02-27 | 2012-01-25 | 埃斯托股份有限公司 | The reaction tubes and the hydrothermal treatment consists that are used for the wet-chemical co-precipitation of oxide powder |
| CN101618889B (en) * | 2009-08-03 | 2011-02-16 | 浙江大学 | Method for preparing lead titanate nano column automatically assembled by perovskite structure nano pieces |
| CN101935216A (en) * | 2010-08-29 | 2011-01-05 | 青岛理工大学 | Method for preparing lithium niobium titanium microwave dielectric ceramic powder by hydrothermal method |
| CN101935216B (en) * | 2010-08-29 | 2014-07-30 | 青岛理工大学 | Method for preparing lithium niobium titanium microwave dielectric ceramic powder by hydrothermal method |
| CN102140694A (en) * | 2011-03-18 | 2011-08-03 | 浙江大学 | Preparation method of barium-doped lead titanate monocrystal nano fiber with one-dimensional column structure |
| CN102718484A (en) * | 2012-06-13 | 2012-10-10 | 广州金升阳科技有限公司 | Preparation method of lead zirconate titanate piezoelectric ceramics |
| CN105424672A (en) * | 2014-09-04 | 2016-03-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Non-stoichiometric oxide SERS substrate and preparation method thereof |
| CN105424672B (en) * | 2014-09-04 | 2019-10-18 | 中国科学院苏州纳米技术与纳米仿生研究所 | Non-stoichiometric oxide SERS substrate and preparation method thereof |
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